Process for treating crude oil.



W. S. BARNICKBL.

PROCESS POB. TREA'IING GRUDE OIL. APPLICATION FILED 111111.13, 1912.

1,093,098. Patented Apr.14,1914.

@fw/Mr. 5* Y a l WILLIAM S. BARNICKEI, OF ST. LOUIS, MISSOURI. ,J

PROCESS FOR TREATING- CBUDE 011th.l

Specification 'of Lettrs Patent.

To all whom it may concern:

.Be 'it known that I, 'WILLIAM S. `BAR5 NICKEL, a citizen of the United States, resid- -ingv at St. Louis, Missouri, have invented a certain new and useful Improvement in Processes for Treatin Crude Oil, of which the following is a fu l, clear, and exact descrip-` tion, such as .will enable others skilled in the art to which it appertains to make and use the same.

This invention relates to the treatment of certain kinds of natural oils, andhas for its object to render such oils'suitable for commercial use.

It not infrequently happens that a well vwill nproduce oil', which is so mixed with v other substances that it is unfit for use and no way hasheretofore been discovered, as far as I am aware, of successfully separating out the oil proper, without the loss of any of the valuable, volatile constituents.

The oils to which I refer are knownin the oil-fields as roily oils, which term I will claimed, is capable of and adapted for use up to 90% or more of foreign matter.

with rgily oils of widely varying percentages of petroleum content, yet it is more particularly adapted and useful for oils containing not less than 10% of foreign matter (slimy substance and water) and from that My' method has proved eminently eflicient land economical in actual practice and, by its use, many thousands of barrels ofk @1L `have been lrecovered from the production of wells which would. otherwise have been i nothing but waste material. v 1 v i It must be clearly understood that the ob-4 ject and result of mymethod are not a mere separation of petroleum-and water, (which may have yemulsifed therewith by accidental addition after the oil has'left the well), but

Y consist in the treatmentl of certain natural oils, as they come from the well, and whichV contain,"besides the water land petroleum, a

V Patenten Apr. 1a, 191e. Application led March 13, 1912. Serial No. 683,619.

relatively large proportion of slimy sub- Y stancethe exact composition of which is unknown to mee-which acts like an emulsifying agent and prevents the natural separation of the petroleum from the water.

VOilspf this kind are thick, viscous liquids, yellow to brownin color, and which -when spread thinly over the ground, look almost like sand. AIn cold weather, it is sometimes so thick that it can be picked up on al shovel, although its consistency depends, of course, upon the Yrelative percentage of petroleum and foreign'matter which it contains. This forelgn matter, when it has been-separated from the petroleum ashereinafter described, conslsts of a slimy, gelatinous mass, of jellylike consistency, and salty water.y Such oils are produced by wells lin the Louisiana, Texas, Oklahoma and California oil-fields, to my own-knowledge, and doubtless occur 1n other/fields. A well will frequently produce good oil for a time and then go bad, in other words, produce roily oiland, as far as Iam aware, no method had been discovered, prior to mine, of treating, such oil commercially so as to render it iii: for transportation and further treatment.

When the percentage of foreign matter is slight, a large part of the petroleum can ybe separated by boiling, but this is an expensive operation and causes a loss of the valuable volatile constituents, such asl gasolene, naphtha, etc. It was also known that sulfuric acid would serve to produce the separation, lbut it is not practicable to use 1t because it combines with the petroleum, ylelding a sulfonated oil which attacks the hence'oil so treated is not marketable. It was lalso known that soluble sulfates, salt, etc., would remove small amounts of water from oil by increasing its specific gravity,

but the problem, which is solved by my process, is' not to separate water from oil in the' presence of each other only, but to isolate the slimy material described above, thus leaving the oil and water free to separate in lthe natural Way.

. I have discovered hat the addition and intimate adfmixture of a very small percentage of a solublefmetallic sulfate to the roily oil, causes'the mixture, vconstituting the latter, tol break promptly, and yield an upper stratum of clear petroleum, a lower -iron of the pipe lines and tank cars and stratum of clear water, and an intermediate'A A stratum of slimy substance between the two;

the

been peculiarly acted upon by the sulfate,

which has caused it to collect together to :form a coherent mass, clearly defined from the strata of petroleum and water.

My experience has been so far that sulfate of iron (copperas) is best adapted for this purpose, both on the score of economy and because it not only acts as a sulfate to eHect the desired separation but also acts to clarify the resulting petroleum and water, combining with other substances, such as carbonate of lime and magncsia, which may be present in the water, and to free the latter from dissolved hydrogen sulfid and oxygen. Other sulfates may, however, be used, although not so advantageously.

In prior processes for separating water from oils by the use of soluble salts, relatively large amounts ofthe latter have been` used, with the object of increasing the specific gravity of the water to such an extent that it will separate from the oil, but in my process, it is only necessary to use relatively very small amounts of the sulfate-as loW indeed, in some cases, as onehundredth of one per cent. of the roily oil being treated-and, furthermore, when the petroleum-is of low gravity, I have frequently found it necessary to add a considerable amount of water, in order to enable the sulfate to permeate all through the liquid. In my process, therefore, as distinguished from the said old processes, I depend upon a peculiar 'action that the sulfate exerts upon the slimy foreign substance present in the oil and which holds it in a state of suspension in the water, which action consists in causing said substance to collect together in a mass, whereby the petroleum is permitted to rise to the top above said mass and the Water to sink to the bottom below the same, and the freed petroleum can readilybe drawn oif.

In the practical operation of my process, I dissolve from 100 to 300 pounds of copperas in one barrel of Water and mix the solution thoroughly with 1,000 barrels of roily oil, preferably heating the mixture to from 100o to o140O I?. The water separates out at once and the slimy substance separates in from eight -to twelve hours. None of the volatile constituents of the petroleum are lost, norany of its constituents affected the petroleum at all.

Naturally many arrangements of apparatus may be used in carrying out my. process and, yin the accompanying drawing, I

have merely represented, 'diagrammaticallyg a simple arrangement, serving to illustrate how the operation is performed.

A represents a tank in which the roily oil is stored as it comes from the well; B a vessel in which. the sulfate is dissolved; C a pumping system by which the oil and sulfate solution are drawn from tank A and vessel B, and which serves at the same time to thoroughly mix the oil and sulfate solution, and D represents the tank into which 'the mixture is delivered and allowed to stand until it has separated into the three I strata of oil, slimy substance and water.

The copperas may be added in powdered form directly to the roily oil and then be thoroughly dissolved and `mixed with the same by agitation, as by introducing steam through perforated pipes E and F, but, in practice, I prefer to mix the sulfate solution with the oil as it is pumped from one tank into another, as the passage through the pumps' and pipes serves to thoroughly mix the liquids. Steam may also be injected into the pipes, as shown at F, for example, to assist in the mixing and to heat the mixture (if the Weather is cold or the oil very thick, for example) or to expedite the process, the essential feature ofwhich is that the sulfate,-in very small relative amount,-be caused to permeate every portion of the oil being treated.

Having thus what I claim is:

LThe process of treating natural emulsions of petroleum, in which the foreign matter amounts to atleast 10% and consists of Water and slimy substances which act `to maintain the water and petroleum emulsified, which consists in intimately mixing therewith a soluble metallic sulfate, in an amount relatively small as compared with the foreign matter, whereby the slimy substances are caused to collect iii anintermediate layer between the Water and the petroleum. p

2.` The process of treating natural oils containing lslimy substances which act to hold the petroleum in suspension in water, which consists in intimately mixing therewith, in the presence of heat, a small percentage of a solution of a metallic sulfate, suchv as sulfate of iron, whereby said slimy substances are caused to collect in a mass and form an intermediate stratum between the freed petroleum and the water.

3. The process of treating natural oils of the kind described, which consists in introducing therein a solution of a metallic described my invention,

sulfate of such strength and quantity that 11 the sulfate will amount to less than 1% of the matter foreign to the oil, thoroughly mixing the same and nally drawing oi the petroleum from the top.

4. The process of treating natural oils of the kind described, which consists in introducing therein a solution of iron sulfate of such strength and quantity that the sulfate will amount to less than 1% o f the matter foreign to the oil, thoroughly mixing the same and finally drawing off the petroleum from the top.

5. The process of treating natural emulsions of oil and Water, containing foreign matter consisting of slimy substances and Water, which substances act to maintain the -oi1 and water emulsifled, and in which such foreign matter amounts to at 'least 10%,

Without in any Way altering its composition, which consists in. intimately mixing therewith a soluble metallic sulfate in an amount relatively small as compared With the amount of foreign matter, and allowing the mixture tol stand,` whereby the slimy substances are caused t0 collect in a mass, and the Water and petroleum are left free to separate. -V

In testimony whereof I hereuntclaiiix my signature in the presence of two Witnesses, this eighth day of March, 1912.

\ a WILLIAM S. BARNICKEL.

Witnesses:

WELLS LCHURCH, GEORGE BAKEWELL.

y for the purposeof recovering the petroleuml 

